1. Technical Field
The present invention relates to fungicidal mixtures, comprising
(1) 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione (prothioconazole) of the formula I or a salt or adduct thereof
and at least one further fungicidal compound, selected from the group consisting of(2) boscalid of formula II
and(3) carboxin of formula III
and(4) metrafenone of formula IV
and(5) a compound of formula V
and(6) a compound of formula VI
and(7) quinoxyfen of formula VII
and(8) dithianon of formula VIII
and(9) thiram of formula IX
and(10) mepiquat chloride of formula X
and(11) cyazofamid of formula XI
and(12) fenoxanil of formula XII
and(13) a compound of formula XIII
and(14) thiophanate-methyl of formula XIV
and(15) carbendazim of formula XV
and(16) metalaxyl of formula XVI
and(17) fludioxonil of formula XVII
and(18) thiabendazole of formula XVIII
and(19) quintozen of formula XIX
and(20) prochloraz of formula XX
and(21) anthraquinone of formula XXI
in a synergistically effective amount.
Moreover, the invention relates to a method for controlling harmful fungi using mixtures of the compounds I and at least one of the compounds II to XXI, and to the use of the compounds I and at least one of the compounds II to XXI for preparing such mixtures, and to compositions comprising these mixtures.
2. Description of the Background Art
Prothioconazole of formula I, i.e. 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]triazole-3-thione, is already known from WO 96/16048.
WO 98/47367 discloses a number of active compound combinations of prothioconazole with a large number of other fungicidal compounds.
Boscalid of formula II and its use as crop protection agent are described in EP-B 0 545 099.
Carboxin of formula III is already known and described in U.S. Pat. No. 3,249,499.
Metrafenone of formula IV is likewise known and described in EP-A-727 141, EP-A 897 904, EP-A 899 255 and EP-A-967 196.
The compound of formula V is described in WO 96/19442.
The compound of formula VI is described in EP-A-1017670, EP-A-1017671 and DE 19753519.4.
Quinoxyfen of formula VII is known from EP-A-0 326 330.
Dithianon of formula VIII is described in GB 857 383.
Thiram of formula IX is described in DE-A-06 42 532.
Mepiquat chloride of formula X is known from DE-A-22 07 575.
Cyazofamid of formula XI is described in PCT/EP/02/00237
Fenoxanil of formula XII is described in PCT/EP/01/14785.
The compound of formula XIII is described in WO 99/56551.
Thiophanate-methyl of formula XIV is known from DE-A-1930540.
Carbendazim of formula XV is described in U.S. Pat. No. 3,657,443.
Metalaxyl of formula XVI is described in U.S. Pat. No. 4,151,299.
Fludioxonil of formula XVII is known from EP-A-206 999.
Thiabendazole of formula XVIII is known from U.S. Pat. No. 3,017,415.
Quintozene of formula XIX is described in DE-A-682048.
Prochloraz of formula XX is described in U.S. Pat. No. 3,991,071.
Anthraquinone of formula XXI is described in The Pesticide Manual, 12th Ed. (2000), page 39.
It is an object of the present invention to provide mixtures which have improved activity against harmful fungi combined with a reduced total amount of active compound applied (synergistic mixtures), with a view to reducing the application rates and improving the activity specetrum of the known compounds I to XXI.
We have found that this object is achieved by the mixture, defined at the outset, of prothioconazole with at least one further fungicide. Moreover, we have found that applying the compound I simultaneously, that is jointly or separately, with at least one of the compounds II to XXI or applying the compound I with at least one of the compounds II to XXI in succession provides better control of harmful fungi than is possible with the individual compounds alone.
2-[2-(1-Chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula I is known from WO 96-16 048. The compound can be present in the “thiono” form of formula I
or in the tautomeric “mercapto” form of formula Ia.

For the sake of simplicity, only the “thiono” form is shown in each case.
Boscalid of formula II
is known from EP-B-0 545 099.
Carboxin of formula III
is known from U.S. Pat. No. 3,249,499.
Metrafenone of formula IV
is known from EP-A-727 141, EP-A-897 904, EP-A-899 255 and EP-A-96 196.
The compound of formula V
is known from WO 96/19442.
The compound of formula VI
is described in EP-A-1017 670, EP-A-1017 671 and DE 197 535 19.4.
Quinoxyfen of formula VII
is known from EP-A-0 326 330.
Dithianon of formula VIII
is described in GB 857 383.
Thiram of formula IX
is known from DE-A-06 42 532.
Mepiquat chloride of formula X
is described in DE-A-22 07 575.
Cyazofamid of formula XI
is described in PCT/EP/02/00237.
Fenoxanil of formula XII
is described in PCT/EP/01/14785.
A compound of formula XIII
is described in WO 99/56 551.
Thiophanate-methyl of formula XIV
is described in DE-A-1 930 540.
Carbendazim of formula XV
is described in U.S. Pat. No. 3,657,443.
Metalaxyl of formula XVI
is described in U.S. Pat. No. 4,151,299.
Fludioxonil of formula XVII
is described in EP-A-206 999.
Thiabendazole of formula XVIII
is described in U.S. Pat. No. 3,017,415.
Quintozene of formula XIX
is described in DE-A-682 048.
Prochloraz of formula XX
is described in U.S. Pat. No. 3,991,071.
Anthraquinone of formula XXI
is described in The Pesticide Manual, 12th Ed. (2000), page 39.